Treatment of hydrocarbons



@Alm JM@ Uw; U? W49 TREA Filed DGO. 1,3, 1945 ATTORNEYS Patented Dec.. 20, 1949 Larga;

TREATMENT OF HYDROCARBONS William W. Weinrich, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application December 13, 1945, Serial No. 634,768

4 Claims.

This invention relates to the treatment ot hydrocarbons. In one of its more specific aspects it relates to the separation and recovery of tertiary base olens from hydrocarbon mixtures containing these and other hydrocarbons.

The present invention is particularly applicable to various refinery streams derived from catalytic or thermal cracking operations. The problem of extracting tertiary olens from such materials has assumed increasing economic importance for two reasons: (1) The intrinsic value of such olefins as chemical intermediates and (2) the deleterious effect of tertiary olefins on certain types of process operations. Tertiary olens are highly reactive and therefore have wide potential applications as comonomers in polymerization reactions and in the manufacture of synthetic rubber modifiers, antioxidants and various useful tertiary alkyl derivatives of organic compounds in the aromatic series. With respect to the purification of hydrocarbon streams, the necessity of removing isobutylene prior to conversion of normal butenes or butane-butene mixtures to butadiene is well established. The employment of anhydrous HC1 in non-catalytic systems is known to the art as a selective reagent for tertiary-base oleiins inthe presence of primary and secondary base olefns. Thus While it is old to react oleiins such as isobutylene in hydrocarbon streams with anhydrous HCl, the recovery of the oleiin from the resulting chloride has not been economically feasible due to the employment of reactions wherein HC1 is chemically combined in various types of compounds.

I have now found that advantage can be taken of the thermal instability of tertiary alkyl chlorides to eiiect substantially complete recovery of olen and HC1 by physical means. This novel separation is accomplished by thermally decomposing a selected tertiary alkyl chloride in the presence of an inert hydrocarbon of lower boiling point than the liberated oleiin while continuously removing from the decomposition zone a vaporous fraction comprising diluent and HC1 and a liquid fraction comprising the recovered olefin.'

One object of my invention is to provide a process for the recovery of tertiary oleiins of 4 or more carbon atoms per molecule from admixtures of said olens with other hydrocarbons.

Another object of my invention is to provide a process for decomposing tertiary alkyl chlorides into tertiary olens and HCl and concomitantly affecting a separation of the decomposition products.

(Cl. 26o-677) vide a combination process for the selective recovery of tertiary olens from hydrocarbon mixtures which involves the formation of tertiary alkyl halides and subsequent thermal decomposition of the segregated halide.

Still another object of my invention is to provide a process wherein the decomposition of a tertiary alkyl halide and the separation of the products formed are accomplished in the same vessel.

Many other objects and advantages will be apparent to those skilled in the art from a careful study of the following disclosure and attached drawing which form a part of this speciiication.

In the drawing the figure represents diagram matically one form of apparatus in which the process of my invention may be practiced.

The present invention is particularly applicable to various renery streams derived from catalytic or thermal cracking operations. In this non-catalytic reaction system tertiary olefins of relatively low molecular weight such as those containing from 4 to 8 carbon atoms, inclusive, are most amenable to treatment. While the more reactive olefins such as isobutylene react readily with HC1 at low pressures, moderately elevated pressures of 20 to 100 pounds per square inch gage are ordinarily preferred for most operations. Since the hydrochlorination reactions and the distillative separation of the resulting alkyl chloride are carried out concurrently in the same tower, operating temperatures are iixed by the' minimum temperature requirements for distillation at the pressures required for hydrochlorination.

' In the recovery of olefin and HC1 from the segregated tertiary alkyl'chloride, ease'oi decompo- Still another object o1 my invention is to pro- 55 sition increases with increasing molecular weight of the alkyl halide. Ordinarily temperatures within the range of 200 F. to 500 F. are adequate for this purpose. To insure substantially complete decomposition of the alkyl halide and to insure that recombination of liberated oleiin and HC1 does not take place, the addition of an inert spacing agent boiling substantially below th'e liberated olefin is added at a rate equivalent to xls-3 moles per mole of tertiary alkyl halide feed. The only limitations prevailing with respect to the selection of a spacing agent are: that it shall be inert toward HC1 at the specified'decomposition conditions; that it shall be condensible at cooling water temperatures under selected operating pressures; and that it shall have a boiling point at least about 20 F. below that ofthe oleiin, Ordinarily, the readily available parain hydrocarbons such as propane, n-butane and npentane are preferred for this purpose a1- though close-cut fractions of natural gasoline are applicable in many instances.

Referring tc the drawing, the major equipment illustrated as suitable for carrying out the process of my invention is more or less standard equipmentfsuch: aszcan' be purchased 'from equipment manufacturers. Such equipmentdncludes a reactor vessel 2, three stripping columns It), 23 and 33 and a fractionator I'I. Smaller equipment parts, yet important are three accumulator vessels 5, 29 and 3l, three coolers 4, I9 and 3Q and a heater I 6. Three pumps "7, if'andare shown. In addition to theselarger single items are piping members, which will be mentioned in the subsequent description :of f the operation. Such auxiliary apparatus as valves, pressure gauges, temperature measuring instrumentsfrecorders, regulators and the like are not shown for .purposes -oi :simplicity .The installation kand .operation of. suchy apparatus .isl well understoody by those'vskilled .in such artxivhen yconsidered in ythe light ofi-the followingdetailed description,

In the operation of .my process; an isobutylenelcontaining C4 hydrocarbon stream such as is .ordinarily available from .xrenery crackingfand dehydrogenation operations 'ischarged 'from a source; not shown,through a line I together with substantially anhydrous HC1 from a line ,35 Ito reactoriZ. .This-freactorzis preferablysa` tower of designr such:thatfhydrochlorination of isobutylene andpdistillative:separation-:of tertiary butyl-.chloride 4'from 'unreacted' .hydrocarbons mayfbe l`affectedaconcomitantly. Isobutylene and Ithe-acid reactsaccording to v.thefollovving equation to? for-m tertiary ibutyl chloride Intheoperation of this reactive and distillative step,` the .column 42 .may be operated. at pressures `up.toabout 10U-pounds per fsquare inch. with a ,v-.- feedinlettemperature ofabout 100 F. To'insure adequatevreflux for-properoperationzand to remoueexcessand unreactedHClvapors at the top of the .columns .are removed 'by fway of an 1. overhead lineV 3 `vand ,passthrough thezcondenser into..theraccurnulatori.tank 5. Hydrogen-chloride admixedwith=some i hydrocarbon vapors f is `Withdrawn continuously? from the'w/apor; section zof' the .accumulatorf bywayaof ;a'1inee6. This vapor is compressed by the compressor l and ypassedthrough aflinef iintothe `recy'cle-I-IClrline `35. AThe condensedthydrocarbonswhichfaccmnuiateinithe Aaccumulator tanlril are. returned to tthe columni 2 Vyro'mtl'ie stripper I0 and'returned by wa-yof aline I I to ,the reactor f column at E:a point rabove Jthe 'takeoff/tray. Y'Inthis upper -sectoncan'd inthe LVkettle since a reboiler coil 4I furnishes heat for .removaleofithe undesirable, more volatile con- Thetertiary butyl chlorideformed in the reactor column 2 becomes concentrated in the stituents. Accordingly, relatively pure tertiary ,butylchloride'is'removed from reactor column 2 "a :decomposer andi-.'fractionator column I 1.

"through,.a'LlinelLand is transferred by pump The-chloride upon "enteringthe column flows ldownward and vbecomes rsubstantially "decomposed "or dissociated so Vthatithe i kettle -material isan` accumulation'of'relativelyhgh boiling poly mers. The dissociation products rise` in the col umn .and 'tenditof recombine in vthe upper zone of lower `temperature. 'At apoint near the feed intaketray; propane'is added tlfiroughV the line .35. HoWever,`;1ittleHCl recombines withthe isobutylene'since the former" is rapidly removed from the zone of reactionby the, high `'vapor pressure l propane. '.The'HC1.-and propanebecome concentrate'd at the top .of .the column .and these mixed vapors are transferred by a -vaporline I8 Vthrough'the condenser. t9 in which. the .propane .is largely condensed. `The .con'fslensate accumulates lin :the accumulator .tank `-.20,...from which vthe T liquid consisting .mainly of ,propane is 4rre- .turndtolthecolunm I1 .by areturnilinell. The

,quantity .-ofvapropane returned to lthe column is governedf by the rate .of addition .of .-thezcooling yvilaterrin condenser vI 9. =.The-vapors removed from the vapor. sectionofi` thisr accumulatoraby Way 'of thenvapor. line.21.contain hydrogen chloriderand propane-and. are ultimately-led to an fHClpurication stepztobedescribed hereinafter.

.Ina decomposer -lressel I 'I `there accumulates a .high."boiling,polymer-material Whichisillltimately -discharged throughiatbottomilinez 24rtoisucludis 'posal asfdesired.

.Isobutylene as :a: 'liquidfisfwithdrawn .from lthe column 5I,- 'I iframes, i :takefoff tray 'i through 1.a.- -line E2 2 fandintroduced into the top fof the stripping column f2 3.

In 1 this Vstripping f column reboiler heatiA from J alcoil '43 `permits removal ofa `rela- .tively pure isobutylene'freefromhydrogen chlorideaan'd propane. "These latter materials return to'fthacolumn Vl'fthrough a vapori-line 325. VThe isobut'ylene passes througha'lineiZ toa storage, 'not'- shown,'or other disposalasdesired.

Feed'- to the propanehydrogen'chlorideseparation andu'ecovery `system is obtained from the 'vaporsection'of theaccurnulatortank'l 20 through linel''hcompressor'28;lineSZS, condenser l'30 and Y tanks l. 'Condensed propane containing dissolved HC1 passes through a .liner` to vtl:1e.;s'trip1: ing vm'rll-ulirlS. "Thiscolumn'is also provided with a reboiler coil 44 for maintaining a sufficiently high temperature so that propane free from HC1 may be withdrawn from the kettle Section of this stripper. The overhead vapors, rich in HC1 are removed from the column through an overhead line 34 and join the material in line 29 just prior to passage through the condenser 30. The kettle product is continuously withdrawn through line 36 and passed to the column l1 for reuse as the HCl and isobutylene separating or spacing agent. Make-up propane may be added to the system through a line 45 provided therefor. Make-up HC1 may be added to the HCl recycle line 35 through a line 3l provided expressly for addition or removal of HCl as needed.

I have found that by operating this HCl-propane recovery column at a pressure of about 400 pounds per square inch and with eicient cooling in the condenser coil 30 adequately concentrated hydrogen chloride may be withdrawn from the top of the accumulator tank 3| for recycle purposes in pipe 35.

When the tertiary olen being separated is isobutylene, I prefer to maintain the kettle material in the decomposer column at a temperature of about 400 F. As mentioned hereinbefore, this kettle temperature will be dependent upon the particular olefin under treatment and somewhat upon the particular inert hydrocarbon spacing agent used. When separating tertiary olens of 4 to 8 carbon atoms per molecule, kettle temperatures for decomposition of the corresponding ter tiary oleiin chlorides will vary from about 200 to a maximum of about 500 F., the lower temperatures being sufficient for the decomposition of the higher molecular weight chlorides since they are more easily decomposed than the lower molecular weight chlorides. The herein described tertiary butyl chloride kettle temperature may be carried at about 400 F. when using propane as a spacing agent. When separating isoamylenes, the C5 tertiary oleiins, butane may be used as the spacing agent since the latter boils at about 31 F. and the C5 tertiary olefins boil at about 88 and 101 F., respectively. Thus for the higher boiling tertiary olefins correspondingly higher boiling spacing agents may be used, the main stipulation being that the spacing agent should preferably boil at least 20 to 25 F. below the lowest boiling olefin separated. Operating pressures need only be those required to maintain proper separation and fractionation conditions within the dissoeiator-fractionator tower.

In the application of this process to a butanebutene stream there is only one tertiary oleiin and one tertiary alkyl chloride to be concerned with. Furthermore, the tertiary chloride formed upon hydrochlorination dissociates into only one olei-ln, isobutylene. In the handling of C5 and higher streams, however, each fraction of substantially constant molecular weight handled will contain two or more tertiary oleiins, and in some cases more than one tertiary alkyl chloride may be formed. Although substantially only tertiary oleiins will react to form chlorides in the rst step of the process, a given higher tertiary chloride can dissociate into more than one olen, not all of which may be tertiary in character. The proportions of the various oleiins formed will depend upon relative rates of reaction and upon the equilibrium conditions prevailing for the particular isomers under consideration. The olens formed, however, will have the same carbon skeleton as found in the tertiary chloride dissociated and as the olen originally occurring in the hydrocarbon fraction treated.

An example of the complex reactions taking place may be cited for the C5 system. There are three isoamylenes which can be present in the C5 fr.; ction. The lowest boiling of the three, 3- metliyl-l-butene (boiling point 68 F.) is not a tertiary olefin and its concentration in the more normal thermally and catalytically cracked streams is very small as compared to that of the other two isoamylenes. 2 methyl 1 butene (boiling point 88 F.) and 2-methyl-2-butene (boiling point 10i F.) are both tertiary olens and will react readily to form the single compound, tertiary amyl chloride. The dissociation of this chloride, however, will yield all three of the isoamylenes mentioned above, although the lowest boiling of the three, B-methyl-l-butene will be present in the product only to a very small extent. The 2-methyl-2-butene will predominate although its concentration in the product may be quite diiierent from its relative concentration to Z-methyl-l-butene in the feed to the process. ln the handling of Cs fractions the picture becomes much more complicated because there are several tertiary oleiins which can form and a correspondingly larger number of dissociated oleiins. can result from dehydrochlorination. Furthermore certain branched chain olens which are not tertiary in character, such as 2-methyl-3- pentene, 4are known to isomerize easily in the presence of acidic materials to the tertiary form 2methyl2pentene, and this latter compound is knownto react readily with HC1 under the condition of this process. It is therefore possible for olens not tertiary in character orginally, but which can become of the tertiary type by a simple shirt in the double bond, to be removed by this process.

When using other spacing agents for the seperation of HCl from another tertiary olen than for the example herein described, the several stripper vessels will best be operated at such pressures and temperatures as will permit the desired separations and as understood by those skilled in such art.

For purposes of simplicity valves, controllers, pressure gauges, recorders and such auxiliary equipment are not shown. Their use is well known.

Since the hydrogen chloride is substantially anhydrous and the hydrocarbon feed stock dry also, corrosion of equipment is at a minimum and therefore, for the most part, ordinary,l standard steel vessels, pipes, pumps and the like may be used.

Since the process, broadly, may be used for the separation of other isoolens, as hereinbefore mentioned, pressures, and temperatures and other operating conditions may be Varied to meet the particular problem at hand as will be understood by those skilled in the art.

Having disclosed my invention, what I desire to claim by Letters Patent is:

1. A process for separating and recovering isobutylene and a butane-n-butene mixture from a hydrocarbon stock containing these materials comprising the steps of contacting the hydrocarbon stock with hydrogen chloride to form tertiary butyl chloride, separating by fractional distillation and as bottoms, said tertiary butyl chloride, removing uncombined hydrogen chloride as fractionator overhead and recycling this hydrogen chloride into said contacting step, and removing a side stream from said fractionation lstepfcomprising a butane-n-butene mixture and some unreacted hydrogen chloride, separating the hydrogen chloride and returning same to the fractionation step and removing the butanen-butene mixture as one product of vthe process; passing said fractionator bottoms comprising tertiary butyl chloride to a decomposer vessel, adding a spacing agent to said tertiary butyl chloride, decomposing said tertiary butyl chloride into an oleiin and hydrogen chloride and separating these two decomposition materials by fractionation in the presence of said spacing agent having a boiling Vpoint to 25 F. below that of the olein, wherein said olefin is separated as one product and the spacing agent and hydrogen chloride are separated as a mixture, further separating said spacing agent from the hydrogen chloride, recycling the latter into the original contacting step, recycling 'the further separated spacing agent into the second separating .Operation, and removing the separated olen'as a productvof the process.

2. The process of cla-im 1 wherein the Aoriginal contacting step for the reaction of hydrogen chloride and isobutylene containing stock .is carried out at a temperature of about 100 F., and the Vdecomposition of the tertiary butyl chloride is carried out at a maximum temperature of about 500 F.

3. A process for separating and recovering'isobutylene and a butane-n-butene mixture from a hydrocarbon stock containing these materials comprising the steps of Ysubjecting said hydrocarbon stock and hydrogen chloride to distillation .conditions at a pressure between the limits of 20 to 100 pounds per square inch, removing from the distillation step tertiary `butyl chloride as bottoms, removing hydrogen chloride as a fractionator overhead and recycling this removed hydrogen vchloride into the fractionation step,

removing a side stream from said fractionation step comprising a mixture of butano, n-butene Vand some hydrogen chloride, separating the hydrogen chloride from the butane-n-butene mixture and returning this hydrogen chloride to said fractionation step and recovering the butanon-butene mixture as one product of the process, subjecting said tertiary butyl chloride to a ,fractional distillation step at a pressure of about 300 pounds per square inch, adding a spacingV agent having a boiling point from 20 to 25 F. below the boiling point of isobutylene to this latter distillation step, removing a mixture comprising isobutylene from this latter distillation step, recovl ering the isobutylene as a second product of the process, removing the spacing agent and hydrogen .chloride mixture from the Vlatter fractional distillation step, separating the hydrogen chloride from the spacing agent and returning the latter to said latter fractional distillation step and the lseparated hydrogen chloride to the rst mentioned fractional distillation step.

4. The process of claim 3 wherein the rst fractional distillation step is carried out at a maximum temperature of F., and the latter fractional distillation step is carried out between the temperature limits of 200 to 500 F., and the spacing agent is propane.

WILLIAM W. WEINRICH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Mar. 24, 1942 2,440,497 Winning et al Apr. 27, 1948 

